WO2008075564A1 - オキシムエステル系化合物、光重合開始剤、光重合性組成物、カラーフィルターおよび液晶表示装置 - Google Patents

オキシムエステル系化合物、光重合開始剤、光重合性組成物、カラーフィルターおよび液晶表示装置 Download PDF

Info

Publication number
WO2008075564A1
WO2008075564A1 PCT/JP2007/073560 JP2007073560W WO2008075564A1 WO 2008075564 A1 WO2008075564 A1 WO 2008075564A1 JP 2007073560 W JP2007073560 W JP 2007073560W WO 2008075564 A1 WO2008075564 A1 WO 2008075564A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
ring
carbon atoms
photopolymerization initiator
general formula
Prior art date
Application number
PCT/JP2007/073560
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Junji Mizukami
Toshiyuki Tanaka
Original Assignee
Mitsubishi Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Priority to KR1020097004732A priority Critical patent/KR101337283B1/ko
Priority to CN200780040202.7A priority patent/CN101528693B/zh
Priority to KR1020137028822A priority patent/KR101477026B1/ko
Priority to KR1020127033270A priority patent/KR101370818B1/ko
Publication of WO2008075564A1 publication Critical patent/WO2008075564A1/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the photopolymerizable composition containing the photopolymerization initiator of the present invention is useful for producing an optical color filter used for a color television, a liquid crystal display device, a solid-state imaging device, a camera and the like. Since the photopolymerizable composition containing the photopolymerization initiator of the present invention is particularly sensitive and excellent in resolution, it is abbreviated as black matrix (Black Matrix 0 or less “BM”) with high definition and high light shielding properties. Force S.) can be manufactured. By using such a photopolymerizable composition, a high-definition and high-quality color filter and liquid crystal display device can be realized.
  • black matrix Black Matrix 0 or less “BM”
  • Force S. can be manufactured.
  • a photopolymerizable composition obtained by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc.
  • a pigment dispersion obtained by dispersing a pigment with a dispersant or the like. Is coated on a glass substrate, dried, exposed using a photomask, and developed to form a colored pattern, which is then heated to fix the pattern to form a pixel. These steps are repeated for each color to form a color filter.
  • Photopolymerizable compositions used for color filter image formation are required to have sufficient resolution, adhesion to a substrate, and low development residue.
  • high color density Therefore, there is a demand for a large pixel and a resin black matrix having a high optical density, and the content of pigments and color materials such as carbon black in the photopolymerizable composition tends to increase.
  • Increasing the content of the color material causes problems such as the above-mentioned resolution, adhesion to the substrate, and developability, and the accuracy and reliability required for color filters as well as a decrease in productivity. It cannot be obtained.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-80068
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2006-53569
  • Patent Document 4 WO2006 / 018405 Publication
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2006-36750
  • the present invention is a photopolymerization capable of easily forming a thin film with a high light-shielding pattern by a photolithography method, and realizing a photopolymerizable composition having sufficient sensitivity and resolution.
  • the primary purpose is to provide an initiator.
  • a photopolymerizable composition containing this photopolymerization initiator it becomes possible to produce a resin BM for a color filter with high accuracy and at low cost.
  • a liquid crystal display device using a color filter produced from the photopolymerizable composition of the present invention has excellent display performance such as contrast.
  • a photosensitive composition for photo spacers and ribs used in the manufacture of liquid crystal display devices
  • photopolymerizable compositions using photopolymerizable materials there is an increasing demand for high-precision and low-cost manufacturing technology, and there is a demand for photopolymerizable image-forming materials with higher sensitivity. Yes.
  • the second object of the present invention is to provide a photopolymerizable composition with higher sensitivity.
  • R 2 is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, an alcohol having 2 to 10 carbon atoms.
  • Xyloxycarbonyl, C7-20 aryloxycarbonyl, C2-20 heteroaryl, C3-20 heteroaryl, or C2-20 alkylaminocarbonyl These groups are! /, And the deviations may also have substituents! /, May! / X represents a divalent aromatic hydrocarbon group and / or aromatic heterocyclic group which may have a substituent and is formed by condensation of two or more rings.
  • the liquid crystal display device of the present invention is characterized by being formed using the color filter of the present invention.
  • R plate and R ⁇ each independently represent a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group.
  • the oxime ester compound of the present invention can be used as a novel and highly sensitive photopolymerization initiator.
  • a photopolymerizable composition useful for color filter applications can be constituted by combining this oxime ester compound with an organic binder and a colorant.
  • a photopolymerizable composition using this oxime ester-based compound in combination with a black pigment as a photopolymerization initiator is excellent in sensitivity and resolution while being highly light-shielding in a thin film.
  • High quality resin BM can be formed.
  • the alkyl group of R 11 and R 12 is preferably an alkyl group having 1 to 10 carbon atoms.
  • the halogen group include Cl, Br, and F.
  • R u and R 12 an alkyl group having 1 to 5 carbon atoms is particularly preferable.
  • a known method can also be used for the addition reaction of the polybasic acid anhydride (c).
  • the addition reaction of polybasic acid anhydride (c) is performed by ⁇ , / 3-unsaturated carbon It can be carried out by continuing the reaction under the same conditions as in the addition reaction of boric acid and / or its ester (b).
  • the addition amount of the polybasic acid anhydride (c) is preferably such that the acid value of the resulting epoxy phthalate resin is in the range of 10 to 150 mg—KOH / g, more preferably 20 to; 140 mg—KOH / g is particularly preferred.
  • the resin acid value is less than the above range, the alkali developability is poor, and when the resin acid value exceeds the above range, a tendency to be inferior in curing performance is recognized.
  • a polyfunctional alcohol such as trimethylolpropane, pentaerythritol or dipentaerythritol may be added to introduce a multi-branched structure.
  • the organic binder (A) the following resins can be used in addition to the epoxide acrylate resin having a carboxyl group obtained as described above.
  • the resins described below include some of those that belong to the epoxy acrylate resin, and are completely different from other substances.
  • styrene (meth) Atari Rate (meth) preferably fitting styrene acrylic acid copolymer 3 to 30 mole 0/0, (meth) Atari rate from 10 to 70 mole 0 / 0 , (Meth) Atallylic acid 10 to 60 mol% Copolymers with a strength of 5 to 25 mol% are more preferred, (Meta) Atallylate 20 to 60 mol%, (Meth) acrylic acid 15 to 55 A copolymer consisting of mol% is particularly preferred.
  • the acid value of these carboxyl group-containing bur resins is usually 30 to 250 mg-KOH / g, preferably 50 to 200 mg KOH / g, more preferably 70 to 150 mg-KOH / g.
  • X represents a divalent aromatic hydrocarbon group and / or aromatic heterocyclic group which may have a substituent and is formed by condensation of two or more rings.
  • the oxime ester-based compound (I) of the present invention can have a high absorbance even when added at a high concentration by making the Y portion a bulky group.
  • Ring X 2 represents a ring condensed with benzene ring X 1 , and may be a single ring or a condensed ring composed of two or more rings. Ring X 2 may be condensed at any position of benzene ring X 1 .
  • the benzene ring X 1 and the ring X 2 fused thereto may further have a substituent.
  • the compound represented by the general formula (i) has a high absorbance and a singlet because the benzene ring X 1 can form a benzophenone structure or a similar structure together with —C ( ⁇ O) —Y. High excitation efficiency from state to triplet state! /, Which is preferable!
  • X in the general formula (I), and as a general formula (i) benzene ring X 1 and ring X 2 is formed in the structure particularly preferred is a group derived from the force carbazole ring. It is preferable that X is a group derived from a carbazole group because it is a robust skeleton in addition to the compatibility with irradiation light during exposure.
  • R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or 4 to 25 carbon atoms.
  • These alkyl groups, alkenyl groups, heteroaryl groups, and heteroarylalkyl groups are! /, All of them have substituents! /, Or may be! /.
  • R 1 as such a group, the sensitivity to light becomes higher compared to a compound in which R 1 is a phenyl group or the like. Ma Since the synthesis of these compounds is also easy, it is preferable from an industrial viewpoint.
  • Examples of the alkyl group having 1 to 20 carbon atoms of R 1 include a methyl group, an ethyl group, a propyl group, and a propyl group, and preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
  • heteroaryl group having 3 to 20 carbon atoms of R 1 examples include thionyl group, furyl group, imidazolyl group, benzthiazolyl group, benzoxazolyl group, preferably 3 to 15 carbon atoms, more preferably carbon. Numbers 4 to 10 are heteroaryl groups.
  • heteroarylalkyl group having 4 to 25 carbon atoms of R 1 examples include thionylmethyl group, furfuryl group, imidazolylmethyl group, benzthiazolylmethyl group, benzoxazolylmethyl group, and the like.
  • R 1 has a substituent! /, May! /, And an alkyl group is particularly preferable! /.
  • an unsubstituted alkyl group is preferable from the viewpoint of ease of production.
  • an alkyl group substituted with a substituted amino group is used from the viewpoint of adhesion of the composition to the substrate.
  • Alkyl groups substituted with N-acetyl-N-acetoxyamino groups are most preferred.
  • Examples of the cycloalkanoyl group having 4 to 8 carbon atoms of R 2 include cyclohexylcarbonyl group, Examples thereof include a cyclohexylcyclohexylcarbonyl group, a cyclopentylcarbonyl group, and the like, and a cycloalkanoyl group having 4 to 8 carbon atoms, more preferably 4 to 7 carbon atoms such as cyclohexylcarbonyl is preferable.
  • alkoxycarbonyl group having 2 to 10 carbon atoms of R 2 examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group, preferably 2 to 10 carbon atoms such as a methoxycarbonyl group, more preferably It is an alkoxycarbonyl group having 2 to 8 carbon atoms.
  • Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms of R 2 include a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, a naphthoxycarbonyl group, and the like, and preferably a naphthoxycarbonyl group and the like. And an arylcarbonyl group having 7 to 15 carbon atoms, more preferably 7 to 10 carbon atoms.
  • heteroarylloyl group having 3 to 20 carbon atoms of R 2 examples include a thiophenecarbonyl group, a pyrrolylcarbonyl group, and a pyridinecarbonyl group, preferably 5 to 15 carbon atoms such as a thiophene carbonyl group, and more preferably.
  • alkylaminocarbonyl group having 2 to 20 carbon atoms of R 2 examples include a morpholinocarbonyl group, a dimethylaminocarbonyl group, a methylaminocarbonyl group, and the like, and preferably a carbon number of 2 such as dimethylaminocarbonyl. To 12, more preferably an alkylaminocarbonyl group having 2 to 10 carbon atoms;
  • R 2 is more preferably an alkanoyl group or a aryloyl group, preferably an alkanoyl group, a cycloalkanoyl or a aryloyl group.
  • the compound represented by the general formula (I) is a compound in which a benzophenone structure or a structure similar thereto easily overlaps with an oxime structure portion due to spatial rotation in the molecule. Therefore, it is preferable because it enables efficient energy transfer within the molecule and achieves higher sensitivity.
  • a condensed ring group formed by condensing one or more rings with a phenyl group at least one selected from the 2,3-position, the 3,4-position and the 4,5-position of the phenyl group
  • the group is preferably a group derived from a 2-4 condensed ring formed by condensing 1 to 3 5- or 6-membered rings.
  • the ring condensed with the phenyl group in Y is preferably a hydrocarbon ring, an aromatic hydrocarbon ring and / or an aromatic heterocyclic ring.
  • the ring condensed with the phenyl group in Y is preferably a hydrocarbon ring from the viewpoint of high quantum yield, and is preferably an aromatic ring from the viewpoint of widening the absorption wavelength.
  • Y include a group derived from an aromatic hydrocarbon ring having two or more condensed rings such as a naphthalene ring, anthracene ring, talycene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, and indene ring, or Examples include groups derived from condensed rings composed of aromatic hydrocarbon rings and aromatic heterocycles, such as atalidine rings, phenanthridine rings, xanthene rings, force rubazole rings, phenazine rings, phenothiazine rings, phenoxazine rings, and benzothiazole rings.
  • Y may be a condensed ring group formed by condensing one or more rings to a monovalent group derived from an aromatic heterocycle.
  • Y in this case is a group derived from “a condensed ring composed of an aromatic hydrocarbon ring and an aromatic heterocycle”, and includes a group in which a bond extends from the aromatic heterocycle.
  • Y is a condensed ring group obtained by condensing one or more rings to a monovalent group derived from an aromatic heterocycle, particularly a benzothiophenyl group, the absorbance of light having a wavelength of 300 nm or less increases. for preferable.
  • a cyclic amino group or a dialkylamino group is particularly preferred.
  • Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; nitro group; cyan group; any organic group.
  • R 3 to R 9 are each independently selected from the group consisting of force S and substituent group Z that are independently selected from a hydrogen atom or substituent group Z.
  • An alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group; having a substituent! /, May! /, An aryl group having 6 to 20 carbon atoms such as a phenyl group; Have a substituent! /, May! /, Carbon number of pyridyl group, etc.
  • R 1 may have, an amino group and an aryl group represented by NR 19 R 2 ° are preferred.
  • R 19 and R 2 ° may be an alkanoyl group which may be substituted, An alkylcarbonyloxy group which may be substituted is preferred.
  • an amino group represented by one NR 19 R 2 ° such as N-acetyl-N-acetoxyamino group is particularly preferred because it is effective for improving the adhesion of the composition! / ⁇ .
  • R 1 represents an alkyl group having carbon atoms;! To 3 or a group represented by the following formula (Ila).
  • one of the oxime ester compounds represented by the general formula (I) may be used alone, or two or more of them may be used in combination. Also good. Further, these oxime ester compounds (I) and other photopolymerization initiators can be used in combination, and in some cases, high sensitivity can be expected by the combined use. Examples of other photopolymerization initiator compounds that can be used in combination with the oxime ester-based compound (I) according to the present invention include the following compounds.
  • an ethylenic compound a compound having one or more ethylenically unsaturated groups
  • an ester of an aliphatic (poly) hydroxy compound and an unsaturated carboxylic acid an ester of an aromatic (poly) hydroxy compound and an unsaturated carboxylic acid, an unsaturated carboxylic acid, a polyvalent carboxylic acid and an aliphatic Polyhide Esters obtained from roxy compounds, ethylene oxides of aromatic polyhydroxy compounds, esterification reaction products of propylene oxide adducts and unsaturated carboxylic acids, ethylene oxides of aliphatic polyhydroxy compounds, and powerful prolataton-modified polyhydric alcohols Unsaturation power Ester with rubonic acid, reaction product of polyhydric alcohol, polyisocyanate and unsaturated carboxylic acid, styryl-terminated compound, phosphoric acid unsaturated compound
  • ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid specifically, ethylene glycol ditalylate, triethylene glycol ditalylate, neopentyl glycol ditalylate, hexanediol Diatalylate, Trimethylol Propanetriatalylate, Trimethylolethane Triatalylate, Pentaerythritol Norresiatalate, Pentaerythritol Triatalylate, Pentaerythritol Tetratallate, Dipentaerythritol Tetratalylate, Dipentaerythritol Acrylates such as penta acrylate, dipentaerythritol hexa acrylate, glycerol acrylate, and other compounds in which the acrylate of these exemplified compounds is replaced with meta acrylate.
  • Acrylic acid ester ether similarly Itakon ester was replaced with it
  • ethylenic compound used in the present invention include acrylamides such as ethylenebisacrylamide; allylic esters such as diaryl phthalate; A bur group-containing compound such as Toto is also useful.
  • ethylenic compounds listed above preferred are those having a (meth) atalyloyl group, and more preferably an atalyloyl group.
  • examples of such compounds include trimethylol-propyl pantriatalylate, trimethylolethane tritalylate, pentaerythritol diacrylate, pentaurisritonotritri acrylate, pentaurislitonoretetraacrylate, dipentaerythritol tetraacrylate, Examples thereof include dipentaerythritol pentaatalylate, dipentaerythritol hexaatalylate, and the like.
  • photopolymerizable monomers may be used alone or in combination of two or more.
  • Dye pigments can be used as the colorant, but pigments are preferred from the viewpoint of heat resistance, light resistance, and the like!
  • pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene
  • various inorganic pigments are also used. Is possible. Specific examples of pigments that can be used are indicated by pigment numbers. Terms such as “C.I. Pigment Red 2” below refer to the color index (C.I.).
  • Blue pigments include C. I. Pigment Fl, Lay 1: 1: 2, 9, 14, 15, 15: 1, 15: 2, 15:
  • green pigments examples include CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 1 8, 19, 26, 36, 45, 48, 50, 51, 54 , 55.
  • C.I. Pigment Green 7, 36 is preferable.
  • black pigment a single black pigment or a black pigment obtained by mixing red, green, blue, or the like can be used. These black pigments can be appropriately selected from inorganic or organic pigments and dyes, and can be used alone or in combination.
  • Cabot Corporation Monarch460, Monarch430, Monarch280, Monarchl20, Monarch800, Monarch4630, REGAL99, REGAL99R, REGAL415, REG AL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS480, PEARLS 130, etc.
  • Titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere and reducing it (JP-A 49-5432), or by high-temperature hydrolysis of titanium tetrachloride.
  • JP-A 49-5432 A method of reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen
  • Japanese Patent Laid-Open No. 57-205322 A method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia
  • JP-A-61-2016 a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (JP-A 61-201610). It is not something to be done.
  • Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, etc., manufactured by Mitsubishi Materials Corporation.
  • the photopolymerizable composition of the present invention is usually blended with (A) an organic binder, (B) a photopolymerization initiator, and (C) a photopolymerizable monomer as needed.
  • the material is used in the state where the optional components described later are dissolved in the solvent (E).
  • the solvent (E) it is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C because each component constituting the composition can be dissolved or dispersed. More preferably, it has a boiling point of 120 ° C; 170 ° C.
  • solvents examples include ethylene glycol monomethyl ether, ethylene glyconomonoethylenoatenole, ethyleneglycolenomonopropinoreatenore, ethylene glyconomonomonobutinoreatenole, ethyleneglycolenomonoethylene Noleyatenore, Propylene Glycole Monomethenoleetenore, Propylene Glyconole T-Butinoreete Nore, Jetty Grenco Gnore Monomethenoleete Nore, Diethylene Glyconole Monomethinore Noete Nore, Metoshi Metino Repentano Nore, Propylene Glycole Monoethylenoleetenole, Dipropylene Glycoleno Monoethylenoleatenore, Dipropylene Glyconole Monomethinoleatenore, 3-Methylenole 3-methoxybutanol, Triprop
  • Etherenoles such as Jetinoreatenore, Dipropinoreatenore, Diisopropinoleatenore, Butinoretenotere, Diaminoleatenore, Etinoreisobutinoreatenore, Dihexinoreatenore;
  • Monohydric or polyhydric alcohols such as ethanolanol, prononoreno, butanol, hexanol, cyclohexanol, ethylen glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
  • aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
  • Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
  • Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid
  • Halogenated hydrocarbons such as butyl chloride and milk mouthride
  • Nitriles such as acetonitrile and benzonitrile
  • the pigment dispersant has affinity for both (D) a coloring material such as a black pigment and (ii) an organic binder, and includes a surfactant such as a nonion, a cation, and an anion, and a polymer dispersant. Equivalent force S.
  • polymer dispersants are particularly preferred. Polymer dispersants having basic functional groups such as primary, secondary, or tertiary amino groups and nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are advantageous. Used for.
  • a preferable chemical structure as a polymer dispersant having a basic functional group include, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule, and the same molecule.
  • resins obtained by reacting active hydrogen with a compound having a tertiary amino group include resins obtained by reacting active hydrogen with a compound having a tertiary amino group.
  • Examples of the above polyisocyanate compounds include aromatics such as paraphenylene diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 4, A 'diphenylenometa.
  • the polyisocyanate is converted to an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carbonates and the like. After the trimerization reaction was stopped by adding a catalyst poison, the unreacted polyisocyanate was removed by solvent extraction and thin-film distillation to contain the desired isocyanurate group. A method for obtaining a polyisocyanate can be mentioned.
  • Examples of the compound having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and alkyl having 1 to 25 carbon atoms at one terminal hydroxyl group of these compounds. And alkoxylated with a group. Moreover, the mixture of these 2 or more types is also mentioned.
  • polyether glycols examples include polyether diols, polyether ester diols, and mixtures of two or more of these.
  • the polyether ester diol includes an ether group-containing diol or other diol.
  • polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycolol, diethylene glycolol, triethylene glycol).
  • Ethylene glycol propylene glycol monoole, dipropylene glycolenole, tripropylene glycolenole, 1,2-butanediole, 1,3-butanediol, 1,4 butanediol, 2,3-butanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyldiol 1,3-propanediol, 1,5-pentanediol 1, 6-hexanediol, 2 methyl-2, 4 pentanedio 2, 2, 4 Trimethyl-1,3 pentanediol, 2 Ethyl-1,3 hexanediol, 2,5 dimethyl-2,5 hexanediol, 1,8-otatamethylene glycol
  • Polyra obtained using 25 monohydric alcohols as initiators examples include tatone diols or polylatatone monools such as poly-force prolataton glycol, polymethylvalerolataton and mixtures of two or more thereof.
  • Most preferred as the polyester glycol is polystrength prolatatone glycol or polystrength prolatatone starting with an alcohol having 1 to 25 carbon atoms.
  • Polycarbonate glycols include poly (1, 6 hexylene) carbonate, poly (3 -Methyl-1,5-pentylene) carbonate and the like, and examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol and the like.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a thio atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group.
  • a hydrogen atom of an amino group is preferred.
  • the tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
  • Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule include N, N dimethylolene 1, 3-propanediamine, N, N jetinole 1, 3-propanediamine, N, N Dipropinoleol 1,3-Propanediamine, N, N Dibutinolei 1,3-Propane Diamine, N, N Dimethinoreethylenediamine, N, N Getinoreethylenediamine, N, N Dipropinoreethylenediamine Min, N, N Dibutynoleethylenediamine, N, N Dimethyl-1, 4 Butanediamine, N, N Jetyl-1, 4 Butanediamine, N, N Dipropyl 1, 4 Butanediamine, N, N—Dibutyl-1, 4, Butanediamine Etc.
  • the tertiary amino group is an N-containing hetero ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, force rubazole ring, indazole ring, benzimidazole ring, benzotriazole ring, N-containing hetero ring such as benzoxazole ring, benzothiazol ring, benzothiadiazole ring, etc.
  • N-containing ring such as 5-membered ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, atrazine ring, isoquinoline ring, etc. Terrorist 6-membered ring.
  • the preferred blending ratio of the dispersant raw material is 100 to 100 parts by weight of the polyisocyanate compound.
  • the number average molecular weight of one or two hydroxyl groups in the same molecule is 300 to 10,000; Parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to; 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.
  • the weight average molecular weight in terms of polystyrene of a polymer dispersant having a basic functional group as measured by gel permeation chromatography (GPC) is 1,000 to 200,000, preferably (or 2,000 to 100 , 000, more preferably (also in the range of 3,000 to 50,000. Basically, if the molecular weight of the polymer dispersant having a functional group is less than 1,000, the dispersibility and dispersion stability are poor, and 200,000 If it exceeds 1, the solubility is lowered, the dispersibility is inferior, and the control of the reaction becomes difficult, and the polymer dispersant is produced according to a known method for producing a polyurethane resin.
  • a solvent for producing a polymer dispersant having a basic functional group usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, Esters such as ethyl acetate, butyl acetate, cellosolve acetate, hydrocarbons such as benzene, toluene, xylene, hexane, some alcohols such as diacetone alcohole, isopropanol, sec-butanol and tert-butanol , Chlorides such as methylene chloride and black mouth form, ethers such as tetrahydrofuran and jetyl ether Aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide are used.
  • ketones such as acetone, methyl ethyl ketone, methyl isobuty
  • a urethanization reaction catalyst is usually used.
  • the urethanization reaction catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltindiotoate, stanasoctate, iron-based compounds such as iron acetyl cetate, ferric chloride, triethylamine, and triethylene.
  • tertiary amines such as diamine.
  • the introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled within the range of 1 to; OOmg- KOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mg—KOH / g.
  • the amine value is a value expressed in mg of KOH corresponding to the acid value after neutralizing titration of a basic amino group with an acid. If the amine value is less than the above range, the dispersibility tends to decrease, and if it exceeds the above range, the developability tends to decrease.
  • the isocyanate group remains in the polymer dispersant by the above reaction. Further, it is preferable to crush the isocyanate group with an alcohol amide compound since the stability with time of the product becomes high.
  • the (B) photopolymerization initiator is usually 0.;! To 50 parts by weight, preferably 1 to 45 parts by weight, based on 100 parts by weight of the (A) organic binder.
  • C) The photopolymerizable monomer is usually used in the range of 0 to 200 parts by weight, preferably 3 to 180 parts by weight, based on 100 parts by weight of the (A) organic binder.
  • the oxime ester compound (I) is preferably contained in an amount of 5 parts by weight or more, particularly 8 to 20 parts by weight, based on 100 parts by weight of the total of (A) the organic binder and (C) the photopolymerizable monomer.
  • the blending amount of the color material (D) such as a black pigment is usually 30 to 70% by weight, preferably 35 to 65% by weight in the total solid content excluding the solvent (E).
  • the compounding amount of the above-mentioned sensitizing dye is usually 0 to 30 parts by weight, preferably 0 to 10 parts by weight with respect to 100 parts by weight of the (A) organic binder.
  • the use ratio thereof is preferably from 0.5% to 30% by weight, particularly preferably from 0.5% to 25% by weight, based on the color material (D).
  • the photopolymerization initiator is less than the above range, the sensitivity is low and the work efficiency may be poor, and if it exceeds the above range, the coating film forming function tends to be adversely affected.
  • the photopolymerizable composition of the present invention has the solid content concentration using the solvent (E) described above.
  • the photopolymerizable composition of the present invention contains a pigment as a coloring material
  • the coloring material is usually dispersed using a paint conditioner, a sand grinder, a bono reminole, a rono reminole, a stone minor, a jet mill, a homogenizer, or the like. It is preferable to do this. Since the coloring material is made fine particles by the dispersion treatment, the coating characteristics of the resist are improved. In addition, when black pigment is used as the color material, it contributes to the improvement of the light shielding ability.
  • dispersion treatment it is preferable to treat in a system in which a black pigment and a solvent or an organic binder having a dispersion function, some! /! Are further used in combination with the above-described pigment dispersant.
  • a polymer dispersant because it is excellent in dispersion stability over time. Dispersion treatment with a solution in which all the components to be blended as a resist solution are mixed at the same time is not preferable because a highly reactive component may be denatured due to heat generated during dispersion.
  • the dispersion condition is usually that the temperature is 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C.
  • the dispersion time varies depending on the composition of the ink (coloring material, solvent, dispersant) and the size of the sand grinder. Adjust accordingly.
  • the standard of dispersion is to control the intensity of the ink so that the 20 ° gloss value of the resist is in the range of 100-200.
  • the dispersion treatment is not sufficient and rough pigment particles are often left unsatisfactory in terms of developability, adhesion and resolution.
  • the dispersion treatment is carried out until the gloss value exceeds the above range, a large number of ultrafine particles are produced, so that the dispersion stability tends to be impaired.
  • the ink obtained by the above dispersion treatment and the above-mentioned other components necessary as a resist component are added and mixed to obtain a uniform solution.
  • fine dust is often mixed with the photosensitive solution, and thus the obtained resist photosensitive solution is preferably filtered with a filter or the like.
  • the photopolymerizable composition of the present invention can be used not only for forming a black matrix in a color filter but also for forming pixels, and for photo spacers (liquid crystal split alignment protrusions) in a liquid crystal display device. It can also be used to form.
  • the photopolymerizable composition of the present invention is applied onto a transparent substrate and dried, then a photomask is placed on the sample, and the photomask is Then, the light shielding resin BM image is formed by image exposure, development, and heat curing or photocuring as necessary, and this operation is repeated for each of the three RGB colors to form one color filter image.
  • a transparent substrate is previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers, and the like. You can also.
  • the method for applying the photopolymerizable composition to the transparent substrate is not particularly limited, but it is usually carried out using a coating apparatus such as a spinner, a wire coater, a flow coater, a die coater, a ronore coater, or a spray.
  • a coating apparatus such as a spinner, a wire coater, a flow coater, a die coater, a ronore coater, or a spray.
  • drying after coating a hot plate, IR oven, competition oven, or the like can be used.
  • Preferred drying conditions are 40 to 150 ° C., and drying time is in the range of 10 seconds to 60 minutes.
  • Light sources used for exposure include, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and other lamp light sources, argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers. And the like.
  • An optical filter can also be used when only a specific wavelength of irradiation light is used.
  • the alkaline developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like.
  • a surfactant e.g., a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, and the like.
  • an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a tetraalkylammonium Mention may be made, for example, of cationic surfactants having a sulfur group.
  • the photopolymerizable composition of the present invention When forming a pixel of a color filter using the photopolymerizable composition of the present invention, it has very high sensitivity and high resolving power, so that exposure and development can be performed without providing an oxygen blocking layer such as polybulual alcohol. Thus, an image can be formed.
  • an alignment film is formed on a color filter, and a spacer is disposed on the alignment film, and then bonded to a counter substrate to form a liquid crystal cell.
  • liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode to complete.
  • the alignment film is preferably a resin film such as polyimide. Gravure is usually used to form alignment films A printing method or a flexographic printing method is employed, and the thickness of the alignment film is usually 10 to 100 nm. After the alignment film is cured by thermal baking, the surface is treated by treatment with a rubbing cloth after being irradiated with ultraviolet rays, and processed into a surface state in which the tilt of the liquid crystal can be adjusted.
  • the spacer a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8111 is preferable.
  • a photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithographic method, and this can be used in place of the spacer.
  • the counter substrate an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.
  • the gap for bonding to the counter substrate is selected in the range of 2 to 8 11 m, which varies depending on the application of the liquid crystal display device.
  • the portions other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin.
  • the sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
  • the liquid crystal cell whose periphery is sealed is cut into panel units, and then the pressure is reduced in the vacuum chamber. After the liquid crystal injection port is immersed in the liquid crystal, the liquid crystal cell leaks in the chamber. Liquid crystal is injected into the cell. Decompression degree in the liquid crystal cell is usually 1 X 10- 2 ⁇ 1 X 10- 7 Pa, preferably from 1 X 10- 3 ⁇ 1 X 10- 6 Pa. Further, the heating temperature at which the liquid crystal cell is preferably heated at the time of depressurization is usually 30 to 100 ° C, preferably 50 to 90 ° C. The warming time during decompression is usually in the range of 10-60 minutes. After that, the liquid crystal cell is immersed in the liquid crystal to inject the liquid crystal. The liquid crystal cell into which the liquid crystal has been injected completes the liquid crystal display device (panel) by sealing the liquid crystal injection port by curing the UV curable resin.
  • the type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of a lyotropic liquid crystal, a thermopick liquid crystal, and the like. Nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, etc. are known for thermo-mouth pick liquid crystal!
  • the photo spacer is formed by applying the photopolymerizable composition of the present invention to a substrate, drying, exposing, developing, and thermosetting.
  • the photopolymerizable composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent.
  • a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like can be used.
  • the die coating method significantly reduces the amount of coating solution used, has no influence from mist adhering to the spin coating method, and suppresses the generation of foreign matter.
  • the coating amount is usually in the range of 0.5 to 10 111, preferably;!
  • the photopolymerizable composition may be supplied in a pattern by an inkjet method or a printing method.
  • the drying after supplying the photopolymerizable composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convex oven. Further, a reduced pressure drying method in which drying is performed in the pressure reducing chamber without increasing the temperature may be combined.
  • the drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying conditions are usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 100 ° C, preferably 50 to 90 ° C, depending on the type of solvent component and the performance of the dryer used. The temperature is selected in the range of 30 seconds to 3 minutes.
  • the exposure is performed by superposing a negative mask pattern on the coating film of the photopolymerizable composition and irradiating an ultraviolet or visible light source through this mask pattern. Further, a scanning exposure method using laser light may be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polybutyl alcohol layer on the photopolymerizable layer.
  • the light source used for the exposure is not particularly limited. Examples of the light source include a xenon lamp, a halogen lamp, and a tungsten lamp.
  • Lamp high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp, etc.
  • Laser sources such as blue-violet semiconductor laser and near-infrared semiconductor laser are listed.
  • An optical filter can also be used when irradiating light of a specific wavelength.
  • the substrate after development is preferably subjected to a thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes.
  • a rib (liquid crystal split alignment protrusion) is a protrusion formed on a transparent electrode in order to improve the viewing angle of a liquid crystal display device. By using the slope of the protrusion, the liquid crystal is locally tilted. The liquid crystal is divided in multiple directions.
  • ribs with the photopolymerizable composition of the present invention three color pixels of BM and RBG are formed, and a color filter and further 150 nm thick ITO are deposited thereon.
  • the photopolymerizable composition of the present invention is coated on a 2 mm thick transparent substrate using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray.
  • the coating thickness of the composition is usually 0.5-5111.
  • a photomask is placed on the dried coating film, and image exposure is performed through the photomask. After the exposure, unexposed uncured portions are removed by development to form pixels.
  • an image after development has a cross-sectional shape close to a rectangular shape.
  • the arched shape necessary for the rib shape it is usually 150 ° C or higher, preferably 180 ° C or higher, more preferably 200 ° C or higher, usually 400 ° C or lower, preferably 300 ° C or lower, More preferably, the heat treatment is performed at 280 ° C. or lower and usually 10 minutes or longer, preferably 15 minutes or longer, more preferably 20 minutes or longer, usually 120 minutes or shorter, preferably 60 minutes or shorter, more preferably 40 minutes or shorter.
  • To change the rectangular cross-sectional shape into an arched shape Form a rib with a width of 0.5 to 20 mm 111 and a height of 0.2 to 5 mm 111.
  • the photopolymerizable composition and heating conditions are adjusted as appropriate, and the contact angle (W1) formed from the side surface of the thin line image (rectangular image cross-sectional shape) before heating and the substrate plane is the above heating temperature.
  • W1 / W2 is usually 1.2 or more, preferably 1.3 or more, more preferably 1.5 or more, Usually, it should be 10 or less, preferably 8 or less. The higher the heating temperature, or the longer the heating time! /, The higher the deformation rate, the lower the heating temperature! The shorter the heating time, or the shorter the heating time, the lower the deformation rate.
  • the bisphenol fluorene type epoxy resin represented by the above formula (a-2) (epoxy equivalent 261) 26 lg was used.
  • Og This was synthesized in the same manner as in Synthesis Example 1 except that the amount was changed to 117 g to obtain a resin having an acid value of 109 mg-KOH / g and a molecular weight of 2600.
  • Tolylene diisocyanate trimer (Mitsubishi Chemical Co., Ltd., Mytec GP750A, resin solid content 50% by weight, butyl acetate solution) 32g and dibutyltin dilaurate 0.02g as propylene glycol monomethyl ether acetate (PGMEA) 47g
  • PMEA propylene glycol monomethyl ether acetate
  • N, N-dimethylamino-1,3-propanediamin lg was added, and the mixture was further reacted at 40 ° C. for 1 hour.
  • the amine value of the solution containing the polymer dispersant thus obtained was determined by neutral titration to be 14 mg-KOH / g.
  • the resin content was 40% by weight as determined by the dry-up method (at 150 ° C for 30 minutes, the solvent was removed on a hot plate and the resin concentration was calculated from the weight change).
  • the mixture was further stirred for 1 hour and 30 minutes.
  • the reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over magnesium sulfate and evaporated to obtain a diketone white solid (10 g).
  • Diketone compound (1.4 g, 3.59 mmol), NH OH-HC1 (0. 261 g, 3.76 mmol), and sodium acetate (0 ⁇ 32 g, 3.9 mmol) were mixed in 15 ml of isopropanol for 3 hours. Refluxed.
  • Synthesis Example 10 Composition of oxime ester compound B-3 The following oxime ester compound (B-3) was synthesized in the same manner as in Synthesis Example 6.
  • A-5; ACA200M manufactured by Daicel Chemical Industries, Ltd. A polymer in which an acrylic monomer having an epoxy group is added to the carboxylic acid group of an acrylic polymer, that is, an acrylic polymer having an acryl group in the side chain)
  • B-8 “OXE-02” manufactured by Chino 'Specialty' Chemicals, Inc.
  • B-9 Compound described in JP-A-20 06-36750.
  • Carbon black for color (Mitsubishi Chemical Co., Ltd., MA-220) 50 parts by weight, the polymer dispersant prepared in Synthesis Example 5 as a solid content at a ratio of 5 parts by weight, so that the solid content concentration is 50% by weight
  • the total weight of the dispersion was 50 g. This was stirred with a stirrer and premixed. Next, dispersion treatment was performed for 6 hours in the range of 25 to 45 ° C. using a paint shaker.
  • the beads used were 0.5 mm diameter Zirco Your beads and the same weight as the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter.
  • each component was added so as to have the following blending ratio as a solid content, and stirred and dissolved with a stirrer to prepare a black resist photosensitive solution.
  • a resist with a low exposure amount is highly sensitive because an image can be formed with a low exposure amount.
  • Minimum pattern dimension is 10 m or less: ⁇
  • Minimum pattern dimension is 10 ⁇
  • the optical density (OD) of the image area was measured with a Macbeth reflection densitometer (manufactured by Kolmorgun, TR927).
  • the OD value is a numerical value indicating the light shielding ability. The larger the numerical value, the higher the light shielding property.
  • Example 1 A-1 ⁇ — 1 7 ⁇ o 3. 8
  • Example 2 A-1 ⁇ -2 6 o ⁇ 3.8
  • Example 3 A-1 ⁇ -3 3 o ⁇ 3. 8
  • Example 4 A-1 ⁇ -4 3 ⁇ ⁇ 3.8
  • Example 5 A-1 ⁇ -5 8 oo 3.
  • Example 6 A-1 ⁇ -6 1 5 o ⁇ 3.8 Implementation Example 7 A-1 ⁇ -7 5 ⁇ 3.8 Example 8 A-2 ⁇ -2 4 ⁇ 3.8 Example 9 A-3 ⁇ -2 4 o ⁇ 3.8 Example 10 A-4 ⁇ — 2 7 o ⁇ 3.8 Example 11 A-6 ⁇ -2 6 ⁇ ⁇ 3.8 Example 12 A-1 ⁇ - 1 0 3 O ⁇ 3.8 Comparative Example 1 A-1 ⁇ -8 20 O ⁇ 3. 8 Comparative Example 2 A-1 ⁇ -9 20 o ⁇ 3. 8
  • Organic binder (A— 4) 46. 6 parts by weight
  • Photopolymerizable monomer (dipentaerythritol hexaatalylate) 6.5 parts by weight
  • Fluorosurfactant (Dainippon Ink Co., Ltd.) 0.0015 parts by weight
  • the above-mentioned clear resist sensitizing solution was glass-coated with a spin coater (manufactured by Coung, 7059). And dried on a hot plate at 80 ° C for 1 minute.
  • the film thickness of the resist after drying was 1 ⁇ m when measured with a stylus type film thickness meter (manufactured by Tencor, Step).
  • a resist pattern was obtained by spray development using a 25% sodium carbonate aqueous solution at a temperature of 25 ° C.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
PCT/JP2007/073560 2006-12-20 2007-12-06 オキシムエステル系化合物、光重合開始剤、光重合性組成物、カラーフィルターおよび液晶表示装置 WO2008075564A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020097004732A KR101337283B1 (ko) 2006-12-20 2007-12-06 옥심에스테르계 화합물, 광중합 개시제, 광중합성 조성물, 컬러 필터 및 액정 표시 장치
CN200780040202.7A CN101528693B (zh) 2006-12-20 2007-12-06 肟酯系化合物、光聚合引发剂、光聚合性组合物、滤色器和液晶显示装置
KR1020137028822A KR101477026B1 (ko) 2006-12-20 2007-12-06 옥심에스테르계 화합물, 광중합 개시제, 광중합성 조성물, 컬러 필터 및 액정 표시 장치
KR1020127033270A KR101370818B1 (ko) 2006-12-20 2007-12-06 옥심에스테르계 화합물, 광중합 개시제, 광중합성 조성물, 컬러 필터 및 액정 표시 장치

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006343065 2006-12-20
JP2006-343065 2006-12-20

Publications (1)

Publication Number Publication Date
WO2008075564A1 true WO2008075564A1 (ja) 2008-06-26

Family

ID=39536197

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/073560 WO2008075564A1 (ja) 2006-12-20 2007-12-06 オキシムエステル系化合物、光重合開始剤、光重合性組成物、カラーフィルターおよび液晶表示装置

Country Status (5)

Country Link
JP (1) JP5151433B2 (enrdf_load_stackoverflow)
KR (3) KR101477026B1 (enrdf_load_stackoverflow)
CN (2) CN101528693B (enrdf_load_stackoverflow)
TW (1) TWI448453B (enrdf_load_stackoverflow)
WO (1) WO2008075564A1 (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008242089A (ja) * 2007-03-27 2008-10-09 Tokyo Ohka Kogyo Co Ltd 感光性組成物
WO2011069947A1 (en) 2009-12-07 2011-06-16 Agfa-Gevaert Photoinitiators for uv-led curable compositions and inks
WO2011069943A1 (en) 2009-12-07 2011-06-16 Agfa-Gevaert Uv-led curable compositions and inks
JP2013101337A (ja) * 2011-10-20 2013-05-23 Mitsubishi Chemicals Corp 着色樹脂組成物、カラーフィルタ、液晶表示装置及び有機ｅｌ表示装置
JP2017501250A (ja) * 2013-11-28 2017-01-12 タコマ テクノロジー カンパニー リミテッドＴａｋｏｍａ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ． 光開始剤及びその感光性組成物
JP2019014884A (ja) * 2017-07-06 2019-01-31 三菱ケミカル株式会社 光重合性組成物、硬化物、画像表示装置及びオキシムエステル系化合物
KR101947474B1 (ko) * 2008-07-09 2019-02-13 도쿄 오카 고교 가부시키가이샤 착색 감광성 수지 조성물 및 옥심계 광중합 개시제
US11947259B2 (en) 2019-06-21 2024-04-02 Igm (Anqing) High Technology Development Co., Ltd Photoinitiator composition containing acylcarbazole derivative and carbazolyl oxime ester, and use thereof in photocurable composition

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009040762A (ja) * 2007-08-09 2009-02-26 Ciba Holding Inc オキシムエステル光開始剤
CN102459171B (zh) * 2009-06-17 2014-07-09 东洋油墨Sc控股株式会社 肟酯化合物、自由基聚合引发剂、聚合性组合物、负型抗蚀剂以及图像图案
WO2011152066A1 (ja) * 2010-06-04 2011-12-08 ダイトーケミックス株式会社 オキシムエステル化合物、オキシムエステル化合物の製造方法、光重合開始剤および感光性組成物
JP6175259B2 (ja) * 2012-03-26 2017-08-02 大阪ガスケミカル株式会社 酸無水物変性フルオレン含有アクリル系樹脂及びその製造方法
KR101664121B1 (ko) 2012-12-13 2016-10-10 제일모직 주식회사 컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터
KR101609634B1 (ko) 2012-12-26 2016-04-06 제일모직 주식회사 감광성 수지 조성물 및 이를 이용한 차광층
KR102281546B1 (ko) * 2013-08-05 2021-07-27 도쿄 오카 고교 가부시키가이샤 안료 분산액, 그것을 포함하는 감광성 수지 조성물 및 분산 조제
CN105531260B (zh) * 2013-09-10 2019-05-31 巴斯夫欧洲公司 肟酯光引发剂
CN106796396B (zh) * 2015-11-02 2018-12-11 互应化学工业株式会社 感光性树脂组合物、干膜和印刷布线板
CN107325206B (zh) * 2016-04-12 2018-12-18 常州强力先端电子材料有限公司 一种含硝基咔唑肟酯类光引发剂及其制备方法和应用
JP6713112B2 (ja) * 2016-04-27 2020-06-24 東京応化工業株式会社 化合物及びその製造方法
KR102532379B1 (ko) * 2018-06-12 2023-05-12 후지필름 가부시키가이샤 광학 이방성층의 제조 방법
CN109233540A (zh) * 2018-08-13 2019-01-18 宁波高新区诠宝绶新材料科技有限公司 一种具有优异热稳定性的聚醚醚酮包线漆新材料的制备方法
CN113518774B (zh) 2019-06-21 2024-10-18 艾坚蒙(安庆)科技发展有限公司 一种新的二芳酰基咔唑化合物及其作为增感剂的应用
KR102743077B1 (ko) * 2022-09-29 2024-12-16 송원산업 주식회사 옥심 에스테르계 광중합 개시제

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06136360A (ja) * 1992-10-29 1994-05-17 Canon Inc 電界発光素子
JP2006036750A (ja) * 2004-02-23 2006-02-09 Mitsubishi Chemicals Corp オキシムエステル系化合物、光重合性組成物及びこれを用いたカラーフィルター
WO2006018405A1 (en) * 2004-08-18 2006-02-23 Ciba Specialty Chemicals Holding Inc. Oxime ester photoinitiators
JP2006053569A (ja) * 2003-06-10 2006-02-23 Mitsubishi Chemicals Corp 光重合性組成物及びこれを用いたカラーフィルター
WO2007062963A1 (en) * 2005-12-01 2007-06-07 Ciba Holding Inc. Oxime ester photoinitiators

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE420877T1 (de) * 2002-12-03 2009-01-15 Ciba Holding Inc Heteroaromatische gruppen enthaltende oximester als photointiatoren
JP2004359639A (ja) 2003-06-06 2004-12-24 Asahi Denka Kogyo Kk オキシムエステル化合物および該化合物を含有する光重合開始剤
TWI285297B (en) * 2004-02-09 2007-08-11 Chi Mei Corp Light-sensitive resin composition for black matrix
JP4839710B2 (ja) * 2004-08-09 2011-12-21 三菱化学株式会社 感光性樹脂組成物、カラーフィルタ及び液晶表示装置
JP4641861B2 (ja) * 2005-05-11 2011-03-02 株式会社Adeka アルカリ現像性樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06136360A (ja) * 1992-10-29 1994-05-17 Canon Inc 電界発光素子
JP2006053569A (ja) * 2003-06-10 2006-02-23 Mitsubishi Chemicals Corp 光重合性組成物及びこれを用いたカラーフィルター
JP2006036750A (ja) * 2004-02-23 2006-02-09 Mitsubishi Chemicals Corp オキシムエステル系化合物、光重合性組成物及びこれを用いたカラーフィルター
WO2006018405A1 (en) * 2004-08-18 2006-02-23 Ciba Specialty Chemicals Holding Inc. Oxime ester photoinitiators
WO2007062963A1 (en) * 2005-12-01 2007-06-07 Ciba Holding Inc. Oxime ester photoinitiators

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008242089A (ja) * 2007-03-27 2008-10-09 Tokyo Ohka Kogyo Co Ltd 感光性組成物
KR101947474B1 (ko) * 2008-07-09 2019-02-13 도쿄 오카 고교 가부시키가이샤 착색 감광성 수지 조성물 및 옥심계 광중합 개시제
WO2011069947A1 (en) 2009-12-07 2011-06-16 Agfa-Gevaert Photoinitiators for uv-led curable compositions and inks
WO2011069943A1 (en) 2009-12-07 2011-06-16 Agfa-Gevaert Uv-led curable compositions and inks
US8569393B2 (en) 2009-12-07 2013-10-29 Agfa-Gevaert N.V. UV-LED curable compositions and inks
US8957224B2 (en) 2009-12-07 2015-02-17 Agfa Graphics Nv Photoinitiators for UV-LED curable compositions and inks
JP2013101337A (ja) * 2011-10-20 2013-05-23 Mitsubishi Chemicals Corp 着色樹脂組成物、カラーフィルタ、液晶表示装置及び有機ｅｌ表示装置
JP2017501250A (ja) * 2013-11-28 2017-01-12 タコマ テクノロジー カンパニー リミテッドＴａｋｏｍａ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．，Ｌｔｄ． 光開始剤及びその感光性組成物
JP2019014884A (ja) * 2017-07-06 2019-01-31 三菱ケミカル株式会社 光重合性組成物、硬化物、画像表示装置及びオキシムエステル系化合物
JP7151215B2 (ja) 2017-07-06 2022-10-12 三菱ケミカル株式会社 光重合性組成物、硬化物、画像表示装置及びオキシムエステル系化合物
US11947259B2 (en) 2019-06-21 2024-04-02 Igm (Anqing) High Technology Development Co., Ltd Photoinitiator composition containing acylcarbazole derivative and carbazolyl oxime ester, and use thereof in photocurable composition

Also Published As

Publication number Publication date
KR101477026B1 (ko) 2014-12-29
KR20130018934A (ko) 2013-02-25
KR20090090296A (ko) 2009-08-25
TWI448453B (zh) 2014-08-11
KR101370818B1 (ko) 2014-03-07
KR20130130872A (ko) 2013-12-02
CN101528693B (zh) 2014-07-02
KR101337283B1 (ko) 2013-12-06
TW200840813A (en) 2008-10-16
CN104030969A (zh) 2014-09-10
JP5151433B2 (ja) 2013-02-27
CN101528693A (zh) 2009-09-09
CN104030969B (zh) 2016-09-07
JP2008179611A (ja) 2008-08-07

Similar Documents

Publication Publication Date Title
WO2008075564A1 (ja) オキシムエステル系化合物、光重合開始剤、光重合性組成物、カラーフィルターおよび液晶表示装置
JP4830310B2 (ja) オキシムエステル系化合物、光重合性組成物及びこれを用いたカラーフィルター
JP7036144B2 (ja) 着色組成物、着色硬化膜、カラーフィルタ、表示素子及び固体撮像素子
CN101805282B (zh) 肟酯化合物、光聚合性组合物和使用该组合物的滤色器
JP2008179611A5 (enrdf_load_stackoverflow)
JP3754065B2 (ja) 光重合性組成物及びこれを用いたカラーフィルター
JP4442292B2 (ja) 光重合性組成物、カラーフィルター及び液晶表示装置
JP5760374B2 (ja) ケトオキシムエステル系化合物及びその利用
JP7451906B2 (ja) 着色樹脂組成物、カラーフィルタ、及び画像表示装置
CN104880910B (zh) 着色组合物、着色固化膜和显示元件
JP6037706B2 (ja) 感光性樹脂組成物、カラーフィルタ及び液晶表示装置
KR20170131415A (ko) 착색 수지 조성물, 컬러 필터, 및 화상 표시 장치
JP2009020501A (ja) カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置及び有機ｅｌディスプレイ
JP2005025169A (ja) 光重合性組成物及びこれを用いたカラーフィルター
JP6620743B2 (ja) 樹脂、感光性樹脂組成物、硬化物、カラーフィルタ及び画像表示装置
JP2013011845A (ja) カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置及び有機ｅｌディスプレイ
KR101434275B1 (ko) 착색 수지 조성물, 컬러 필터, 액정 표시 장치, 및 유기 ｅｌ 디스플레이
KR102361882B1 (ko) 착색 조성물, 착색 경화막 및 표시 소자
JP2005148717A (ja) カラーフィルター用着色組成物、カラーフィルター及び液晶表示装置
JP4911205B2 (ja) 光重合性組成物、カラーフィルター及び液晶表示装置
KR100783337B1 (ko) 옥심 에스테르 화합물, 광중합성 조성물 및 이것을 사용한컬러 필터
KR101760147B1 (ko) 감광성 수지 조성물, 컬러 필터 및 액정 표시 장치

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780040202.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07850176

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1020097004732

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07850176

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1020127033270

Country of ref document: KR